1,3-substituted 1, 1, 3, 3-tetrachloro 1, 3-disilapropane



i 'atented June 26, 1951 1,3 SUBSTITUTED 1,1,3,3 -TETRACHLORO 1,3-DISILAPROPANE Harold A. Clark, Midland, Mich, assignor to Dow CorningCorporation, Midland, Mich., a corporation of Michigan No Drawing.Application March 19, 1949, Serial No. 82,471

Claims. I

The present invention relates to the production of new organosiliconcompounds and to the fluids so produced.

The present organosilicon industry is based upon siloxanes which arematerials in which the silicon atoms are linked through oxygen atoms.Another type of compound is one in which the silicon atoms are linkeddirectly to each other. Still a third type is one in which the siliconatoms are linked by organic radicals. The literature presents verylittle information on this last ty ie of compound.

One object of the present invention is to produce organosiliconcompounds in which the silicon atoms are linked by methylene radicals.Still other objects and advantages of the present invention will beapparent from the following description.

The compounds hereof are of the type YzRSiCI-IzS-lRYz where each Rrepresents a hydrocarbon radical of the group consisting of alkylradicals such as methyl to octadecyl and monocyclic aryl radicals, suchas phenyl, tolyl and xylyl, and each Y represents a substituent of thegroup consisting of alkoxyl and halogen preferably ethoxyl, chlorine orbromine. These compounds are of the types The present compounds may beprepared by reacting a compound of the type XzRSiCI-IzSiXs with aGrignard reagent of the type RMgX. In the above type formulae each Xrepresents a halogen atom and each R represents an alkyl or a monocyclicaryl radical. The intermediate compound X2RSiCI-I2S1X3, is disclosed in70 JACS 3590, at page 35%.

In the Grignard coupling reaction, the Grignard reagent is used inamount of from 0.5 and 1.5 mole per mol of XzRSiCHZSiXs whereby toreplace one of the halogens with alkyl or monocyclic aryl radicals.

The products of the present invention are of utility as Water-proofingagents. The products hereof are also of substantial importance asintermediates in the production of other organosilicon products. Thus,upon hydrolysis and condensation, products are obtained which containboth methylene and siloxane bridges between the silicon atoms. These areof use for preventing foaming in aqueous and non-aqueous systemscontaining organic materials.

Emample 1 When methyl Grignard reagent, CHsMgBr, in amount of 119 partsin ether solution is gradually added to 262.5 parts ofClzCHzSiCI-IzSlCla, a coupling reaction occurs. The reactants arecooled, the products filtered, and the ether is removed in a strippingstill. The product CIzCHsSiCHzSiCHsClz,

may be separated by distillation. This product has a boiling point of192 C. at atmospheric pressure and a density of 1.288 at 25 C.

A mixture of 242 parts of this product, C12CI-I3SiCH2SiCI-I3C12 and 47.8parts of CsI-IsCHaSiClz in 310 parts of toluene was added to 699 partsof H20 over a period of one-half hour at 5-28 C. 190 parts of toluenewere then added to make 25% resin solids in toluene solution. The resinwas washed 4 times with 50 C. water and 3 times with cold H2O. Then, thetoluene was stripped from the resin. The resin cures in less than onehour at C. The resin also maintained satisfactory flex for longer thanhours at 250 C.

Example 2 1410 parts by weight of phenyl Grignard reagent, C6H5MgBr, inether solution was added to 1312.5 parts of ClsSiCI-IcSiClzCI-Ie and themixture added to 1100 parts of toluene. The reactants were cooled, theproducts filtered, and. the ether removed in a stripping still. 387parts of the product, CsHsClcSiC'I-IzSiClzCI-Ia, was separated bydistillation. This compound was found to have a boiling point of 148.5"C. at 13 mm, a refractive index of 1.5290 at 25 C., a density or" 1.313at 25 (3., and a specific refraction of 0.3084.

That which is claimed is:

1. Compositions of the general formula in which R represents a radicalof the group consisting of alkyl and monocyclic aryl radicals.

3. ClzCHsSiCI-IzSiCI-IsClz 4. The method which comprises reacting acompound of the type C12CH3SiCI-I2S1Cl3 in liquid phase with a compoundof the type RMgX in which R represents a radical of the class consistingof alkyl and monocyclic aryl radicals and X represents a halogen atom,the latter compound being employed in proportion between 0.5 and 1.5mols per mol of the former, whereby a product of the formulaClzCHzSiCfizSiRClz is ob- Goodwini "Jour. Chem. Soc. v01. 69, pa etamed. 2247.

5. The method in accordance with claim 4 in Bluestein: Jour; Am. Chem.800.; vol. 70, which R represents methyl. pages 3068-3071.

HAROLD A. CLARK. 5 Sauer et a1.-: Jour. Am. Chem. Soc.; vol. '70 (1948)pages 3590-3596. REFERENCES CITED The following references are of recordin the file of this patent:

1. COMPOSITIONS OF THE GENERAL FORMULA